Compositions, textiles treated therewith and processes for the treatment thereof



Melvin D. Hurwitz, Huntingdon Valley, Pa., assignor to Rohm & HaasCompany, Philadelphia, Pa, 21 corporation of Delaware N Drawing.Application June 21, 1955 Serial No. 517,062

'14 Claims. (Cl. 260-675) This invention relates to compositions for thetreatment of textile materials, and it is particularly concerned withthe treatment of textile materials of cellulosic type to improve theircharacteristics, especially to render the fabrics resistant to crushingand to shrinkage on laundering. It is also concerned with the treatedfabrics thereby obtained and with methods for treating fabrics with thenovel compositions.

Heretofore, condensates of formaldehyde with melamine, urea, and cyclicurea derivatives, such as N,N- ethyleneurea and N,Ntrimethyleneurea havebeen applied to cellulosic fabrics, such as cotton, for the purpose ofimparting crush-resistance and reduced shrinkage on laundering. However,fabrics treated with these condensates pick up chlorine during bleachingoperations using chlorine, such as those using it in the form of ahypochlorite. On ironing the fabrics that have been bleached in thismanner, severe discoloration and/ or loss in tensile and/ or tearstrengths have generally resulted. In those cases where severediscoloration is encountered, the treatment with these condensates isunsuitable when a white fabric is ultimately desired. In some cases, asmuch as 90% loss in strength is encountered as a result of the action ofheat as in ironing, on fabrics treated with these condensates andbleached with chlorine. The presence on a fabric of a thermosetcondensate of formaldehyde with melamine frequently gives rise to somediscoloration of the fabric on the mere treatment with a hypochloritebleach, unless care is taken to avoid excess chlorine and elevatedtemperatures. Ironing in such cases serves to aggravate thediscoloration.

It has also been suggested, for crease-proofing cellu- States Patent 0losic fabrics, to apply polymethylol-tetrahydro-s-triazones 1substituted in the '5-position, such asdimethylol-S-methyltetrahydro-s-triazone-Z. However, fabrics treatedtherewith develop an unpleasant odor unless extreme care is taken towash out by-products after the curing thereof on the fabric. Inaddition, the fabrics treated therewith frequently show discoloration onheating or ironing whether or not the fabrics have been treated withchlorine before the heating or ironing is efliected. The fabric leavesthe curing stage in distinctly yellow condition. Heating afterchlorination aggravates this yellowing severely.

It has been suggested in US. Patent 2,690,404 to combine amelamine-formaldehyde condensate with a dimethylol ethyleneurea in aneffort to reduce the discoloration and loss of strength of cellulosicfabrics treated with such condensates on bleaching and ironing. However,the improvement obtained by this combination of condensates is generallyrelatively insignificant and the proportions in which the twocondensates may be employed are quite narrow in range.

In accordance with the present invention, it has been discovered thatcellulosic fabrics, such as cotton and the like, can be treated, toeffect crease-proofing and so on without encountering serious odors,discoloration, and loss of strength, with an aqueous solution containingin 2,901,463 Patented Aug. 25, 1959 certain proportions (-1) acondensate of formaldehyde with melamine, urea, N,N-ethyleneurea, andN,N-trimethyleneurea (which will be termed hereinafter Component A),with (2) a compound of Formula I following (which will be termedComponent B):

where R is selected from the group consisting of 2-hydroxyethyl,2-methyl-2-hydroxyethyl, and alkyl groups having 1 to 4 carbon atoms.

It has been found in accordance with the invention that theincorporation of at least- 25 mole percent and not over mole percent ofa compound of Formula I (Component B) in a mixture comprising suchcompound and a condensate of formaldehyde with melamine, urea,N,N-ethyleneurea and N,N-trimethyleneurea (Component A) overcomes thedisadvantages of discoloration and loss in strength of fabrics treatedtherewith that are normally encountered on heating after chlorinationwhen any of these formaldehyde condensates are applied alone inaccordance with the prior art. In addition, the odor normally associatedwith fabrics on which a triazone condensate has been cured is minimized.When less than 25 mole percent of the triazone condensate is employed,the improvements in respect to discoloration and loss of tensilestrength are inappreciable, and when more than 75 mole percent isemployed, the benefits in these factors are substantially reduced. Formost purposes, from the standpoint of cost, cfliciency, freedom fromdiscoloration, and low tensile loss on ironing or heating afterchlorination, it is preferred to use from 30 to 50 mole percent ofComponent B and from 70 to 50 mole percent respectively of Component A.

Examples of the tetrahydro-s-triazones that may be employed includedimethylol-5-methyl-tetrahydro-s-triezone-2, dimethylol 5hydroxymethyl-tetrahydros-triaZone-Z,dimethylol-5-ethyl-tetrahydro=s-triazone-2,dimethylol-5-n-propyl-tetrahydro-s-triazone-Z, dimethylol-S-isopropyl-tetrahydro-s-triazone-2,dimethylol-S-t-butyltetrahydro-s-triazone2,dimethylol-5-n-butyl-tetrahydros-triazone-Z, dimethylol 5 sec butyltetrahydro-s-triezone-2. These methylol derivatives may be termed adimethylol-tetrahydrostriazone-Z, and the condensate used may includethe specific clear-cut compounds named or it may include a mixture ofcompounds containing the dimethylol compound. In any event, theformaldehyde condensates of this type may be obtained in known manner,such as by the condensation of a mixture of from 2 to 5 moles andpreferably at least 2.5 moles of formaldehyde per mole of thetetrahydrotriazone in an aqueous solution thereof. The condensation maybe effected at a pH of 6 to 8 at a temperature of 30 to 120 C. andprefermably between about to 210 C. The extent of condensation and thecomple tion of the desired reaction may be controlled by varying thetime and temperature.

As Component A, any water-soluble condensates of formaldehyde withmelamine, urea, N,N'-ethyleneurea or N,N'-trimethyleneurea may beemployed. Examples of specific compounds that may be used includedimethylolurea, trimethylolmelamine, dimethylol-N,N'-ethyleneurea, anddimethylol-N,N'-trimethyleneurea. In addition, the alkylated derivativesof these polymethylol condensates obtainedfrom thelower alcohols frommethyl through butyl may be employed. Examples includedimethoxymethylurea, diethoxymethylurea, dimethoxymethyl-N,N-ethyleneurea, and so on. Again, it should be noted that the condensatesemployed as Component A may be fairly sharply defined compoundsincluding those just named as well as others, :or it may comprisemixtures of compounds of varying degrees of substitution wherein thenumber of methylol groups or alkoxymethyl groups may be different in theseveral compounds within the mixture.

The aqueous solution of the Water-soluble condensates, includingComponent A and Component B, may contain such condensates in aconcentration in about 2% to 25% or more, based on total condensatesolids. The particular concentration applied in any given instance maydepend on the purpose for which the condensate mixture is applied and onthe particular substrate or fabric to which it is applied. In the caseof cotton, the concentration is preferably from 2% to 12%, whereas inapplication to rayon the concentration is preferably to 20%, when thepurpose of the application is to impart crease-resistance,crush-resistance, or shrinkage stabilization.

While it is generally unnecessary, Component A and Component B may bereacted together provided any such reaction leaves the final condensatein a Water-soluble condition. However, for most purposes, it ispreferred not to co-react these components.

The solution containing the mixture of condensates (Component A andComponent B) or the co-reacted condensates is stable when subjected toordinary conditions of storage and can be sold, shipped, and stored assuch. Shortly before use, the acidic catalyst may be added, if desired,as pointed out hereinafter.

An acidic catalyst is applied to the fabric either simultaneously withthe condensates or before or after the mixture of condensates isapplied. Preferably the acidic catalyst is dissolved in the aqueoussolution of the mixture of condensates. Suitable catalysts includeammonium phosphate, ammonium thiocyanate, hydrochloric or other acidsalts of a hydroxy aliphatic amine including Z-methyl-Z-amino-l-propanol, 2-methyl-2-amino-1,3-propandiol, tris(hydroxymethyl) aminomethane, Z-phenyl-Z-amino-l propanol,2-methyl-2-amino-l-pentanol, Z-aminobutanol, triethanolamine,2-ami-no-2-ethyl-l-butanol, also ammonium chloride, pyridinehydrochloride, benzyldirnethylamine oxalate. The catalyst is generallyintroduced into the aqueous solution of the condensates at aconcentration of about /2 to 2% and preferably approximately 1%.

The compositions of the present invention may be applied to fibers,filaments, yarns, or fabrics of cellu-losic type and especially those ofcotton or rayon for various purposes. For example, they may be appliedsimply to modify the feel or texture of the surface of the fabrics. Whenapplied in greater quantities, the condensates of the present inventionmay be used to stiffen the fabrics and to make them wrinkle-resistant,crush-resistant and crease-resistant. The application of increasingamounts of the condensates serves to provide proportionately increasedreduction in shrinkage of the treated fabric on laundering, and whenabout 3% to 8% by weight of the condensate, based on the weight of thefabric, is applied, the cellulosic fabric is generally substantiallystabilized against shrinkage on laundering. The application of thecondensates of the present invention may be employed for the purpose ofaiding embossing operations. They may also be applied to fabrics as partof a process for their conversion to pliss fabrics.

The aqueous solution of the condensates may be applied by spraying,brushing, dipping, as in padding, or by roller-coating. After theapplication, excess may be removed, as by squeezing or squeegeeing. Thetreated fabric is then dried, suchas by air-drying at room temperatureor by the treatment with heated air up to temperatures of about 212 F.

After the fabric has been dried, the condensate mixture is baked orcured on the fabric at a temperature of about 220 to 450 F. or higher,depending on the particular substrate. The time may be varied generallyin inverse proportions to the temperature. For example, the time mayvary from about five seconds to half an hour. A time of 30 seconds at400 F. is quite practical and a time of 15 to 30 minutes at 220 F. isgenerally satisfactory. The baking operation may simply be acontinuation of the drying operation so that drying and curing maybeeffected in essentially a one-stage procedure.

The drying and/ or the baking may be effected by any suitable means forapplying the heat, such as by the application of heated air currents, byinfra-red radiation or by high frequency electric induction.

In the following examples which are illustrative of the invention, theparts given are by weight unless otherwise noted: The A.A.T.C.C.chlorination test referred to in the examples involves the treatmentwith a hypochlorite solution containing 025% available chlorine at atemperature of 77 F.i2 F. for 15 minutes with intermittent stirring.This treatment is followed by rinses in six fresh water baths at 70 to80 F. with a squeeze between rinses and drying in air at roomtemperature. The drying is followed by conditioning for at least fourhours at 70 F. and 65% relative humidity. The percentage loss in tensilestrength referred to hereinbelow is calculated by the formula where t isthe tensile strength after chlorination only and t is the tensilestrength after both chlorination and ironing (or scorch test).

EXAMPLE 1 (a) A solution is made up in water containing 4.5% ofdimethylol-S-methyl-tetrahydro-s-triazone-Z and 1.25% ofdimethylol-N,N-ethyleneurea and 0.5% of ammonium chloride. A bleachedcotton fabric is padded through this solution. After draining excess anddrying at 240 F. for five minutes, the fabric is cured at 300 F. for tenminutes. Chlorination is carried out under A.A.T.C.C. conditions aboveand the fabric is ironed at 365 F.i2 F. for 30 seconds (the standardA.A.T.C.C. scorch test). The ironed fabric is conditioned at 70 F. and65 relative humidity for at least four hours before testing forstrength.

(b) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is reduced to 3% and theconcentration of dimethylol- N,N-ethyleneurea is increased to 2.5%.

(c) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is reduced to 1.5% and theconcentration of dimethylol- N,N-ethyleneurea is increased to 3.75%.

(d) The procedure of part (a) here is repeated except that theconcentration of the triazone derivative is reduced to zero and theconcentration of dimethylol-N,N'- ethyleneurea is increased to 5.0%.

(e) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is increased to 6% and theconcentration of dimethylol- N,N'-ethyleneurea is reduced to zero. 7

In each of parts (a) to (d) inclusive of Example 1, the totalconcentration of formaldehyde condensate is equivalent in molarity tothat in each other part. The mole ratio of the Component A to ComponentB in part (a) is 1:3, in part (b) is 1:1, and in part (c) is 3:1.

Table I shows the comparative results of the procedures described inparts (a) to (e) inclusive of Example 1. In the crease-recovery test, Wis the angle of return in the warp, and F is the angle of return in thefill as measured by the Shirley crease-recovery test.

(a) A solution is made up in water containing 4.5% ofdimethylol--methyl-tetrahydro-s-triazone-2 and 1.5%

.of a low molecular Weight condensate of methanol, formaldehyde, andurea comprising largely dimethoxymethylurea and 0.5% of ammoniumchloride. A bleached cotton fabric is padded through this solution.After draining excess and drying at 240 F. for five minutes,

the fabric is cured at 300 F. for ten minutes. Chlorination is carriedout under A.A.T.C.C. conditions above and the fabric is ironed at 365F.i2 F. for 30 seconds (the standard A.A.T.C.C. scorch test). The ironedfabric is conditioned at 70 F. and 65% relative humidity for at leastfour hours before testing for strength.

(b) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is reduced to 3.0% and theconcentration of the urea condensate is increased to 3.0%.

(c) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is reduced to 1.5 and theconcentration of the urea condensate is increased to 4.5%.

(d) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is reduced to zero and theconcentration of the urea condensate is increased to 6.0%.

(e) The procedure of part (a) hereof is repeated except that theconcentration of the triazone derivative is increased to 6.0% and theconcentration of the urea condensate is reduced to zero.

In each of parts (a) to (e) inclusive of Example 2, the totalconcentration of formaldehyde condensate is equivalent in molarity tothat in each other example. The mole ratio of the Component A toComponent B in part (a) is 1:3, in part (b) is 1:1, and in part (c) is3:1.

Table II shows the comparative results of the procedures described inparts (a) to (e) inclusive of Example 2.

The procedure of Example 1 (a) is followed except that the triazone isreplaced with 2.0% of dimethylol-S-S-hydroxyethyl)-tetrahydro-s-triazone-2 and the concentration of thedimethylol-N,N'-ethyleneurea is increased to 3.75%. The discolorationand loss in tensile strength after chlorination and ironing iscomparable to those of Example 1(a).

EXAMPLE 4 The procedure of Example 2(a) is repeated except that theconcentration of the triazone derivative is 3.0% and the condensate isreplaced with 3.0% of diethoxymethylurea. After chlorination andironing, the fabric exhibits only a slight discoloration, and thetensile loss is comparable to that of Example 1(a).

EXAMPLE 5 The procedure of Example 1(a) is repeated substituting for thetriazone derivative 3.4% of dimethylol-S- ethyl-tetrahydro-s-triazone-2and for the ethyleneurea derivative 3.0% of dimethylol N,N'trimethyleneurea. After chlorination and ironing, only a slightdiscoloration is evident and the tensile loss is comparable to thatobtained in Example 1(a).

EXAMPLE 6 The procedures of Examples 1(a) and 1(c) are repeated on ableached rayon fabric. In each case, even less evidence of discolorationis obtained and less tensile loss is caused by the chlorination andironing procedures than is obtained in Examples 1(a) and (c) on thecotton.

EXAMPLE 7 The procedure of Example 1(a) is repeated using 2.5% ofdimethylol-S-(fl methyl-fl-hydroxyethyl)-tetrahydro-striazone-2 andreplacing the ethyleneurea with 3.5% of trimethylolmelamine. Thecrease-proofed fabric, after chlorination and ironing exhibits a slightdiscoloration and a loss of tensile strength comparable to that obtainedin Example 1(a).

It is to be understood that changes and variations may be made Withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

I claim:

1. A composition comprising an aqueous solution of a mixture of 25 to 75mole percent of a compound of Formula I:

I O (i HOCHzN NCHzOH H; CH,

where R is selected from the group consisting of 2-hydroxyethyl,2-methyl-2-hydroxyethyl, and alkyl groups having 1 to 4 carbon atoms,and 75 to 25 mole percent respectively of a Water-soluble condensate offormaldehyde with N,N-ethyleneurea.

2. A composition comprising an aqueous solution containing a mixture of25 to 75 mole percent of dirnethylol- 5-methyl-tetrahydro-s-triazone-2,and 75 to 25 mole percent respectively of a water-soluble condensate offormaldehyde With N,N'-ethyleneurea.

3. A composition comprising an aqueous solution containing a mixture of25 to 75 mole percent of dimethylol-S-(fl-hydroxyeth-yl)-tetrahydro-s-triazone-2, and 75 to 25 mole percentrespectively of a Water-soluble condensate of formaldehyde withN,N-ethyleneurea.

4. A composition comprising an aqueous solution containing a mixture of25 to 75 mole percent of dimethylol- 5-ethyltetrahydro-s-triazone-2, and75 to 25 mole percent respectively of a Water-soluble condensate offormaldehyde With N,N'-ethyleneurea.

5. A composition comprising an aqueous solution containing a mixture of25 to 75 mole percent of dimethylol-5-(B-rnethyl-B-hydroxyethyl)-tetrahydro-striazone-2, and 75 to 25 molepercent respectively of a water-soluble condensate of formaldehyde withN,N'-ethyleneurea.

6. A composition comprising an aqueous solution of a mixture of 25 to 75mole percent of dimethylol-S-methyl-tetrahydro-s-triazone-2 and 75 to 25mole percent of dimethylol-N,N-ethyleneurea.

7. A composition comprising an aqueous solution of a mixture of 30 to 50mole percent of dimethylol-S-meth- 7 yl-tetrahydro-s-triazoner2 and 70to 50 mole percent of dimethylol-N,N'-ethyleneurea.

8. An article of manufacture comprising a cellulosic textile fabricmodified by a reaction product of a mixture of 25 to 75 mole percent ofa compound of Formula I:

NCHIOH where R is selected from the group consisting of 2-hydroxyethyl,2 methyl-2-hydroxyethy1, and alkyl groups having 1 to 4 carbon atoms,and 75 to 25 mole percent respectively of a water-soluble condensate offormaldehyde with N,N'=ethyleneurea.

9. 'An article of manufacture comprising a cellulosic textile fabricmodified by a reaction product of a mixture of 25 to 75 mole percent 'ofdirnethylol-S-methyl-tetrahydro-s-triazone-2 and 75 to 25 mole percentrespectively of dimethylol-N,N-ethyleneurea.

10. A process for treating a fabric comprising applying to a cellulosictextile fabric an aqueous solution of a mixture of 25 to 75 mole percentof a compound of Formula I:

HO OHllN HOCHzN NCH OH H: CH:

N l R where R is selected from the group consisting of 2-hydroxyethyl,2-methyl-2-hyd'roxyethyl, and alkyl groups having 1 to 4 carbon atoms,-and 75 to 25 mole percent respectively of a Water-soluble condensate offormaldehyde with N,N-ethyleneurea, applying an acidic catalyst to thefabric, and drying and curing the condensates at 8 a temperature of 220F. to 450 F. on the treated fabric.

11. A process for treating a fabric comprising applying to a cellulosictextile fabric an aqueous solution containing 2% to 25% of a mixture ofcondensates comprising 25 to moles percent ofdimethylol-S-methyltetrahydro-s-triazone-Z and 75 to 25 mole percentrespectively of dimethylol-N,N-ethyleneurea, applying an acidic catalystto the fabric, and drying and curing the condensates on the treatedfabric at a temperature of 220 F. to 450 F.

'12. A composition comprising an aqueous solution containing a mixtureof 25 to 75 mole percent of dimethylol-S-(B-hydroxyethyl)-tetrahydro-s-triazone-2, and 75 to 25 mole percent ofdimethylo1-N,N'-ethyleneurea.

13. An article of manufacture comprising a cellulosic textile fabricmodified by a reaction product of a mixture'of 25 .to 75 mole percent ofdimethylol-S-(fi-hydroxyethyl) -tetrahydro-s-triazone-2, and 75 to 25mole percent of dimethylol-N,N'-ethyleneurea.

14. A process for treating a fabric comprising applying to a cellulosictextile fabric an aqueous solution containing 2% to 25% of a mixture ofcondensates comprising 25 to 75 mole percent ofdimethylol-S-(fi-hydroxyethyl)-tetrahydro-s-triazone-2 and 75 to 25 molepercent respectively of dimethylol-N,N'-ethyleneurea, applying an acidiccatalyst to the fabric, and drying and curing the condensates on thetreated fabric at a temperature of 220 F. to 450 F.

References Cited in the file of this patent UNITED STATES PATENTS2,049,217 M'eunier July 28, 1936 2,321,989 Burke June 15, 1943 2,373,135Maxwell Apr. '10, 1945 2,641,584 Martone r June 9, 1953 2,690,404Spangler et al Sept. 28, 1954 2,826,500 Keim Mar. ll, 1958 FOREIGNPATENTS 291,473 Great Britain June 1, i928

1. A COMPOSITION COMPRISING AN AQUEOUS SOLUTION OF A MIXTURE OF 25 TO 75MOLE PERCENT OF A COMPOUND OF FORMULA 1: